EP0004877B1 - A process for thermally polymerizing cyclic phosphazenes - Google Patents

A process for thermally polymerizing cyclic phosphazenes Download PDF

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Publication number
EP0004877B1
EP0004877B1 EP19790100883 EP79100883A EP0004877B1 EP 0004877 B1 EP0004877 B1 EP 0004877B1 EP 19790100883 EP19790100883 EP 19790100883 EP 79100883 A EP79100883 A EP 79100883A EP 0004877 B1 EP0004877 B1 EP 0004877B1
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catalyst
compound
cyclic
polymerization
cocatalyst
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EP19790100883
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German (de)
French (fr)
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EP0004877A1 (en
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Dennis Laverne Snyder
Jung Wong Kang
John William Fieldhouse
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Bridgestone Firestone Inc
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Firestone Tire and Rubber Co
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00Nitrogen; Compounds thereof
    • C01B21/082Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/097Compounds containing nitrogen and non-metals and optionally metals containing phosphorus atoms
    • C01B21/098Phosphonitrilic dihalides; Polymers thereof
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00Nitrogen; Compounds thereof
    • C01B21/082Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/097Compounds containing nitrogen and non-metals and optionally metals containing phosphorus atoms
    • C01B21/098Phosphonitrilic dihalides; Polymers thereof
    • C01B21/0986Phosphonitrilic dichlorides; Polymers thereof

Definitions

  • This invention relates to a process for thermally polymerizing cyclic phosphazenes represented by the general formula (NPHal 2 ) n in which Hal is a halogen selected from Cl, F and Br and n is an integer from 3 to 7 comprising heating said cyclic phosphazenes to a temperature in the range between 150 and 300°C to produce a linear polydihalophosphazene wherein the degree of polymerization is between 20 and 50,000.
  • the invention- relates to the use of suitable catalysts in order to improve the above polymerization by increasing the rate of polymerization, while decreasing or entirely eliminating the formation of gel and by permitting better control of the molecular weight and other physical properties of the polymer produced.
  • the polymerization vessels In scaling-up such methods of thermal polymerization from laboratory size glass apparatus to pilot plant and semiworks installations, the polymerization vessels have been fabricated from stainless steels because of the relatively high temperatures utilized in the polymerization.
  • An object of this invention is to conduct a catalyzed polymerization of cyclic dichlorophosphazene oligomers at temperatures well below 205°C and preferably as low as 170°C so that such polymerizations can be effected in glass-lined equipment instead of in stainless steel reaction vessels and to prepare linear polydichlorophosphazene polymers having relatively low dilute solution viscosities in high yields from trimer, tetramer and other low molecular weight cyclic oligomers of NPCI Z .
  • This object is accomplished by the invention by conducting said heating to thermally polymerize said cyclic phosphazene in the presence of a catalytically effective amount of a catalyst-compound of a transition metal selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W.
  • the amount of catalyst present is between 0.1 millimoles and 20.0 millimoles/mole of cyclic phosphazene.
  • the desired polymerization of cyclic dichlorophosphazenes to linear polydichlorophosphazenes can be effected at lower temperatures and at a more rapid rate by the use of catalyst compounds of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo or W. It has also been found that the catalyzed polymerizations in glass or in stainless steel vessels proceed without the formation of gel, and that the molecular weight of the product can be controlled conveniently by varying the concentration of catalyst. It has further been found that some control over the molecular weight distribu l ion of the resulting polymer can be achieved by incremental addition of the catalyst and/or of the cyclic oligomers to the polymerization apparatus.
  • Catalysts' suitable for the present invention are generally produced by preparing suitable compounds of one or more transition elements of Groups IV, V or VI, particularly metal halides, metal hydrides or metal alkyls of the transition element. It appears that transition elements which form compounds with incomplete d-shells and are in the lower valence states can associate metal alkyls to form complexes with highly polarized bonds.
  • catalysts for the present invention are compounds of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W wherein at least some of the metal is present in a valence state of 3 or below, or is associated with a sufficient amount of a reducing agent, capable of lowering the valence of such metal to the lower valence state.
  • Metals, metal hydrides, metal alkyls or aryls and Grignard reagents are examples of the reducing agents which may be present to lower the valence of the transition metal in the compound which is to act as a catalyst.
  • the transition metal compounds which serve as catalysts or from which the catalyst is prepared may be inorganic compounds such as a halide, oxyhalide, or other complex halide, or oxide or may be organic compounds such as an alcoholate, acetate or phenolate.
  • Particularly preferred metals are titanium, zirconium, vanadium and chromium.
  • TiCl 3 , TiCl 4 , ZrCl 4 , VCl 5 and CrCl 3 are such compounds.
  • Ziegler type catalysts i.e. combinations of such compounds with organometallic compounds of aluminum or boron represented by the formula R a MX b in which M is either Al or B having a valence of a+b: X is anionic, e.g. a halogen such as chlorine and R is a hydrocarbon selected from the group consisting of alkyl, aryl, cycloalkyl, alkaryl and arylalkyl.
  • cyclic trimer (NPCl 2 ) 3 and the indicated additive were charged into small, clean, dry, glass tubes in a dry box.
  • the sealed tubes and their contents were placed in a forced air oven maintained at the desired temperature and polymerized for the times shown in Table I.
  • the polymerizates are then removed from the glass tubes and unreacted trimer was removed by sublimation.
  • Unsublimed material is the polymer which can then be dissolved in benzene or toluene and reacted with alkoxides as described in US-A-Patents 3,370,020 or 3:515,688 noted above. A control without the additive was also run at the same time.
  • catalysts may comprise the compounds of metals of Groups IVB, VB, and VIB of the Periodic Table or combinations of such catalysts with cocatalysts such as compounds of B or AI. This is further shown in the following table.
  • the triethyl aluminum was used as 20% solution in toluene, and the vanadium acetylacetonate as a 0.1 molar solution.
  • the product can be recovered in any of several ways.
  • a preferred method is to permit the reactor to cool sufficiently whereupon the polydichlorophosphazene can be dissolved in a solvent or solvent mixture and the product can be flushed out of the reactor.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Description

  • This invention relates to a process for thermally polymerizing cyclic phosphazenes represented by the general formula (NPHal2)n in which Hal is a halogen selected from Cl, F and Br and n is an integer from 3 to 7 comprising heating said cyclic phosphazenes to a temperature in the range between 150 and 300°C to produce a linear polydihalophosphazene wherein the degree of polymerization is between 20 and 50,000.
  • More particularly, the invention- relates to the use of suitable catalysts in order to improve the above polymerization by increasing the rate of polymerization, while decreasing or entirely eliminating the formation of gel and by permitting better control of the molecular weight and other physical properties of the polymer produced.
  • Thermal polymerization of (NPCl2)n where n is a small integer such as 3 or 4 are described in US-A 3,370,020, US-A 3,515,688 and elsewhere in the literature. GB-A 1,506,835 describes a process for polymerizing cyclic (NPCl2)n which comprises heating the polydichlorophosphazene in the presence of a catalyst comprising a Lewis acid to produce a substantially linear (NPClz)m polymer.
  • In scaling-up such methods of thermal polymerization from laboratory size glass apparatus to pilot plant and semiworks installations, the polymerization vessels have been fabricated from stainless steels because of the relatively high temperatures utilized in the polymerization.
  • An undesired consequence of the use of stainless steel equipment has been the contamination of the polymerization mixture with small amounts of metals such as chromium, nickel and iron which have significant but unpredictable effects on the manner in which the polymerization proceeds. Owing to the corrosive nature of some of the materials present, this effect is accentuated by higher temperatures. It has been found that results of polymerizations in stainless steel reactors are different from results of polymerizations in glass and that gelation of the linear polydichlorophosphazene polymer products becomes a serious problem in stainless steel equipment.
  • Consequently much effort has been directed toward effecting the polymerization of cyclic dichlorophosphazenes at lower temperatures than those described in the prior art, since the use of glass-lined equipment is more feasible at lower temperatures. The use of glass-lined equipment is generally considered practical at temperatures up to about 205°C.
  • An object of this invention is to conduct a catalyzed polymerization of cyclic dichlorophosphazene oligomers at temperatures well below 205°C and preferably as low as 170°C so that such polymerizations can be effected in glass-lined equipment instead of in stainless steel reaction vessels and to prepare linear polydichlorophosphazene polymers having relatively low dilute solution viscosities in high yields from trimer, tetramer and other low molecular weight cyclic oligomers of NPCIZ.
  • The catalyzed polymerizations of dichlorophosphazene oligomers in stainless steel reactors should be conducted without the formation of any substantial gelled product.
  • This object is accomplished by the invention by conducting said heating to thermally polymerize said cyclic phosphazene in the presence of a catalytically effective amount of a catalyst-compound of a transition metal selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W.
  • According to a preferred embodiment of the present invention the amount of catalyst present is between 0.1 millimoles and 20.0 millimoles/mole of cyclic phosphazene.
  • According to the present invention it has been found that the desired polymerization of cyclic dichlorophosphazenes to linear polydichlorophosphazenes can be effected at lower temperatures and at a more rapid rate by the use of catalyst compounds of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo or W. It has also been found that the catalyzed polymerizations in glass or in stainless steel vessels proceed without the formation of gel, and that the molecular weight of the product can be controlled conveniently by varying the concentration of catalyst. It has further been found that some control over the molecular weight distribulion of the resulting polymer can be achieved by incremental addition of the catalyst and/or of the cyclic oligomers to the polymerization apparatus.
  • Catalysts' suitable for the present invention are generally produced by preparing suitable compounds of one or more transition elements of Groups IV, V or VI, particularly metal halides, metal hydrides or metal alkyls of the transition element. It appears that transition elements which form compounds with incomplete d-shells and are in the lower valence states can associate metal alkyls to form complexes with highly polarized bonds.
  • Particularly preferred catalysts for the present invention are compounds of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W wherein at least some of the metal is present in a valence state of 3 or below, or is associated with a sufficient amount of a reducing agent, capable of lowering the valence of such metal to the lower valence state. Metals, metal hydrides, metal alkyls or aryls and Grignard reagents are examples of the reducing agents which may be present to lower the valence of the transition metal in the compound which is to act as a catalyst.
  • The transition metal compounds which serve as catalysts or from which the catalyst is prepared may be inorganic compounds such as a halide, oxyhalide, or other complex halide, or oxide or may be organic compounds such as an alcoholate, acetate or phenolate.
  • The following compounds are illustrative of preferred catalysts which may be used in the practice of the present invention.
  • Metal halogen compounds of metals of Groups IVB, VB, and VIB of the Periodic Table represented by the formula M'Y'c in which c is the valence of the metal M; and Y is anionic, e.g. a halogen such as chlorine. Particularly preferred metals are titanium, zirconium, vanadium and chromium. TiCl3, TiCl4, ZrCl4, VCl5 and CrCl3 are such compounds.
  • Ziegler type catalysts, i.e. combinations of such compounds with organometallic compounds of aluminum or boron represented by the formula RaMXb in which M is either Al or B having a valence of a+b: X is anionic, e.g. a halogen such as chlorine and R is a hydrocarbon selected from the group consisting of alkyl, aryl, cycloalkyl, alkaryl and arylalkyl.
  • The invention will be more fully understood from the Examples which follow and which are intended to illustrate and not to limit the invention.
  • Twenty (20) grams of cyclic trimer (NPCl2)3 and the indicated additive were charged into small, clean, dry, glass tubes in a dry box. The tubes were then evacuated to a vacuum of 0.1 mm Hg (=0.1 xO.00133322 bars) or less and sealed while connected to the vacuum line. The sealed tubes and their contents were placed in a forced air oven maintained at the desired temperature and polymerized for the times shown in Table I. The polymerizates are then removed from the glass tubes and unreacted trimer was removed by sublimation. Unsublimed material is the polymer which can then be dissolved in benzene or toluene and reacted with alkoxides as described in US-A-Patents 3,370,020 or 3:515,688 noted above. A control without the additive was also run at the same time.
  • Tables I and II illustrate the results obtained with different starting materials.
    Figure imgb0001
  • As indicated in Table II above, catalysts may comprise the compounds of metals of Groups IVB, VB, and VIB of the Periodic Table or combinations of such catalysts with cocatalysts such as compounds of B or AI. This is further shown in the following table. The triethyl aluminum was used as 20% solution in toluene, and the vanadium acetylacetonate as a 0.1 molar solution.
    Figure imgb0002
  • The product can be recovered in any of several ways. A preferred method is to permit the reactor to cool sufficiently whereupon the polydichlorophosphazene can be dissolved in a solvent or solvent mixture and the product can be flushed out of the reactor.
  • Although the invention has been described with specific reference to dichlorophosphazenes it is also applicable to the polymerization of dibromophosphazene and difluorophosphazene oligomers.

Claims (10)

1. A process for thermally polymerizing cyclic phosphazenes represented by the general formula (NPHal2)n in which Hal is a halogen selected from the group consisting of Cl, F and Br and n is an integer from 3 to 7 comprising heating said cyclic phosphazenes to a temperature in the range between 150 and 300°C to produce a linear polydihalophosphazene wherein the degree of polymerization is between 20 and 50,000, characterized by conducting said heating to thermally polymerize said cyclic phosphazene in the presence of a catalytically effective amount of a catalyst-compound of a transition metal selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W.
2. The process of claim 1 wherein Hal is CI and n is 3,4 or mixtures of 3 and 4.
3. The process of claim 1 wherein the catalyst includes a cocatalyst which is a compound of AI or B.
4. The process of claim 1 in which the amount of catalyst present is between 0.1 millimoles and 20.0 millimoles/mole of cyclic phosphazene.
5. The process of claim 1 in which the catalyst is a metal halogen compound.
6. The process of claim 1 in which the catalyst is a Ti compound.
7. The process of claim 1 in which the catalyst is TiCI3 or TiCl4.
8. The process of claim 1 in which the catalyst is ZrCl4.
9. The process of claim 1 in which a cocatalyst is present in addition to the catalyst and the cocatalyst is an organometallic compound RaAIXb, in which R is alkyl, aryl, cycloalkyl, arylalkyl or alkylaryl and a and b are small integers totalling the valence of AI and X is anionic.
10. The process of claim 1 in which the catalyst further contains an aluminum alkyl compound.
EP19790100883 1978-04-20 1979-03-23 A process for thermally polymerizing cyclic phosphazenes Expired EP0004877B1 (en)

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US89800778A 1978-04-20 1978-04-20
US898007 1978-04-20

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EP0004877B1 true EP0004877B1 (en) 1982-05-12

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55123624A (en) * 1979-03-16 1980-09-24 Otsuka Chem Co Ltd Production of phosphagene polymer
US4412053A (en) * 1981-02-09 1983-10-25 Neilson Robert H Polyphosphazene compounds and method of preparation
US4708858A (en) * 1985-04-17 1987-11-24 The Dow Chemical Company Polymerization of cyclic dihalophosphazene oligomers
US20060264967A1 (en) 2003-03-14 2006-11-23 Ferreyro Roque H Hydraulic device for the injection of bone cement in percutaneous vertebroplasty

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* Cited by examiner, † Cited by third party
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GB1506835A (en) * 1975-08-22 1978-04-12 Firestone Tire & Rubber Co Catalysis of phosphazene cyclics to polymer using lewis acids
US4080432A (en) * 1975-08-22 1978-03-21 The Firestone Tire & Rubber Company Dissolution of polydihalophosphazenes
US4116891A (en) * 1976-12-06 1978-09-26 Armstrong Cork Company Catalytic process for the preparation of phosphazene polymers
CA1109636A (en) * 1977-04-18 1981-09-29 Mark S. Prichard Metal salt catalyzed polymerization of (npcl.sub.2) oligomers

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EP0004877A1 (en) 1979-10-31
AU4602979A (en) 1979-10-25
AU523868B2 (en) 1982-08-19
JPS5516076A (en) 1980-02-04

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